CN118993848A - Method for producing 1, 3-butanediol product - Google Patents
Method for producing 1, 3-butanediol product Download PDFInfo
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- CN118993848A CN118993848A CN202411004269.7A CN202411004269A CN118993848A CN 118993848 A CN118993848 A CN 118993848A CN 202411004269 A CN202411004269 A CN 202411004269A CN 118993848 A CN118993848 A CN 118993848A
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- C07—ORGANIC CHEMISTRY
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- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
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- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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Abstract
本发明涉及1,3‑丁二醇制品的制造方法。所述方法包括：将粗1,3‑丁二醇与水和有机溶剂在5℃～80℃的温度下混合，使得相分离成水层与有机层后，获得包含1,3‑丁二醇的水层的萃取工序；对所述包含1,3‑丁二醇的水层在60℃～130℃的温度下进行20分钟～9小时加热处理的水解工序；从所述加热处理后的包含1,3‑丁二醇的水层中将水蒸馏除去的脱水蒸馏工序；和从所述将水蒸馏除去后的1,3‑丁二醇中将低沸点成分蒸馏除去的脱低沸蒸馏工序，所述有机溶剂为选自由脂肪族烃、芳香族烃、醚、有机氯化物、酯、酮组成的组中的一种以上。
The present invention relates to a method for manufacturing a 1,3-butanediol product. The method comprises: mixing crude 1,3-butanediol with water and an organic solvent at a temperature of 5°C to 80°C, so that the phase is separated into an aqueous layer and an organic layer, and then obtaining an extraction process of an aqueous layer containing 1,3-butanediol; a hydrolysis process of heating the aqueous layer containing 1,3-butanediol at a temperature of 60°C to 130°C for 20 minutes to 9 hours; a dehydration distillation process of distilling water from the aqueous layer containing 1,3-butanediol after the heat treatment; and a de-low boiling distillation process of distilling low-boiling components from the 1,3-butanediol after the water is distilled off, wherein the organic solvent is one or more selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ethers, organic chlorides, esters, and ketones.
Description
The present invention is a divisional application of Chinese patent application with the application number 202280006633.6, the application date 2022, the 5 month and 18 days and the name of 1, 3-butanediol product.
Technical Field
The present invention relates to a1, 3-butanediol product useful as a raw material for synthetic resins, a raw material for surfactants, a solvent, an antifreeze, a raw material for cosmetics, and the like.
Background
1, 3-Butanediol is a viscous colorless transparent odorless liquid with a boiling point of 208 ℃ and has excellent chemical stability. Therefore, 1, 3-butanediol is used as a raw material for various synthetic resins and surfactants. In addition, 1, 3-butanediol is also used as a material for cosmetics, moisture absorbent, high boiling point solvent, antifreeze, and the like, because of its excellent moisture absorption property, low volatility, and low toxicity. In particular, in the cosmetic industry in recent years, there has been a great increase in demand for nontoxic, non-irritating 1, 3-butanediol having excellent properties as a humectant.
Patent document 1 discloses 1, 3-butanediol having a low odor. Further, as a method for obtaining 1, 3-butanediol having a low odor, a method for producing 1, 3-butanediol comprising the step of mixing crude 1, 3-butanediol with water and an organic solvent to separate the phases into an aqueous layer and an organic layer and then obtaining an aqueous layer containing 1, 3-butanediol is disclosed. In the production method of this document, the organic solvent used as the extractant may be a ketone, and methyl isobutyl ketone is more preferable.
[ Prior Art literature ]
[ Patent literature ]
[ Patent document 1] Japanese patent laid-open No. 2003-96006
Disclosure of Invention
[ Problem to be solved by the invention ]
However, the method described in patent document 1 has a problem that it is difficult to completely eliminate the odor, and if stored for a long period of time, a slight odor is generated due to the change with time.
In addition, when 1, 3-butanediol is used in the cosmetic field, it is sometimes formulated by heating under alkaline conditions, but 1, 3-butanediol obtained by the method described in patent document 1 also has a problem that coloration occurs during the mixed preparation under alkaline conditions.
In view of the above, an object of the present invention is to provide a1, 3-butanediol product which is odorless and does not generate odor with time and is less likely to generate coloration under alkaline conditions.
[ Means for solving the problems ]
The present inventors have conducted intensive studies and as a result, have found that the above problems can be solved by suppressing the concentration of a specific impurity contained in 1, 3-butanediol to a constant level or less, and have completed the present invention.
Namely, the present invention is as follows.
[1]
A1, 3-butanediol product, wherein the weight ratio calculated from the sum of the absorbance of the peaks of 2, 4-dinitrophenylhydrazine derivatives of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane is 90 ppm or less in HPLC analysis under the following conditions after the preparation of the following sample.
[ Preparation of sample ]
2, 4-Dinitrophenylhydrazine was extracted by adding acetonitrile 5mL to a 2, 4-dinitrophenylhydrazine cartridge (INERTSEP MINI AERO DNPH, GL Sciences Co.), 1000. Mu.L of the resulting solution and 0.2 mol/L of hydrochloric acid 100. Mu.L were added to 1, 3-butanediol preparation 0.05 g and the reaction was carried out at 45℃for 2 hours.
[ Conditions for HPLC analysis ]
Measuring a sample: the reaction solution obtained by the sample preparation was diluted to 2 mL with the mobile phase used in HPLC, and the diluted solution was used as a measurement sample.
A detector: ultraviolet-visible (UV-Vis) detector
Detection wavelength: 369 nm (nm)
Analytical column: column with palmitoamidopropyl modified silica gel (particle size 5 μm, inner diameter x length=4.6 mm ×25 cm, pore size 100 a, surface coverage 2.7 micromole/m 2, surface area 450 m 2/g, metal impurities less than 5 ppm, carbon content 19.5%) as stationary phase
Analysis conditions: column temperature 40 DEG C
Mobile phase: acetonitrile/distilled water=50/50 (volume ratio)
Mobile phase flow rate: 0.4 mL/min
Sample injection amount: 20. mu L (mu L)
Calibration curve: is prepared by using dinitrophenylhydrazine derivatives of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane which are synthesized separately.
[2]
The 1, 3-butanediol product according to the above [1], wherein the weight ratio calculated from the sum of the absorbance of the peaks of the 2, 4-dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane is 75 ppm or less.
[3]
The 1, 3-butanediol product according to the above [1] or [2], wherein a weight ratio calculated from a sum of absorbance of peaks of the 2, 4-dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane is 60 ppm or less.
[ Effect of the invention ]
The present invention provides a1, 3-butanediol product which is odorless and does not generate odor with time and is not easy to generate coloring under alkaline conditions.
Drawings
FIG. 1 is a graph of HPLC analysis after the 1, 3-butanediol of example 1 was previously reacted with 2, 4-dinitrophenylhydrazine reagent.
FIG. 2 is a graph of HPLC analysis after the 1, 3-butanediol of comparative example 1 was previously reacted with a2, 4-dinitrophenylhydrazine reagent.
Detailed Description
Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following description, and can be variously modified within the scope of the gist thereof.
In the present embodiment, 1, 3-butanediol as a final product is also referred to as "1, 3-butanediol product", and 1, 3-butanediol as a raw material is referred to as "crude 1, 3-butanediol".
The 1, 3-butanediol product of the present embodiment is a1, 3-butanediol product having a weight ratio (hereinafter, also simply referred to as "peak and weight ratio") of 90 ppm or less calculated from the sum of the absorbance of the peaks of the 2, 4-dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane in HPLC analysis under specific conditions after the reaction with the 2, 4-dinitrophenylhydrazine reagent in advance. The 2, 4-dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane is a compound obtained by derivatizing impurities contained in 1, 3-butanediol with 2, 4-dinitrophenylhydrazine (hereinafter, also referred to as "DNPH"). In addition, in the HPLC analysis under the following specific conditions, when the relative retention time of the peak of DNPH is 1.0, the peak of the derivative appears as peak a and peak B having a relative retention time in the range of 1.1 to 1.6 (see fig. 1 and 2).
The measurement conditions for HPLC analysis in this embodiment are as follows.
[ Preparation of sample ]
2, 4-Dinitrophenylhydrazine was extracted by adding acetonitrile 5mL to a 2, 4-dinitrophenylhydrazine cartridge (INERTSEP MINI AERO DNPH, GL Sciences Co.), 1000. Mu.L of the resulting solution and 0.2 mol/L of hydrochloric acid 100. Mu.L were added to 1, 3-butanediol preparation 0.05 g and the reaction was carried out at 45℃for 2 hours.
[ Conditions for HPLC analysis ]
Measuring a sample: the reaction solution obtained by the sample preparation was diluted to 2 mL with the mobile phase used in HPLC, and the diluted solution was used as a measurement sample.
A detector: ultraviolet-visible light detector
Detection wavelength: 369 nm (nm)
Analytical column: column with palmitoamidopropyl modified silica gel (particle size 5 μm, inner diameter x length=4.6 mm ×25 cm, pore size 100 a, surface coverage 2.7 micromole/m 2, surface area 450 m 2/g, metal impurities less than 5 ppm, carbon content 19.5%) as stationary phase
Analysis conditions: column temperature 40 DEG C
Mobile phase: acetonitrile/distilled water=50/50 (volume ratio)
Mobile phase flow rate: 0.4 mL/min
Sample injection amount: 20. mu L (mu L)
Calibration curve: is prepared by using dinitrophenylhydrazine derivatives of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane which are synthesized separately.
Here, for example, SUPELCO (registered trademark) Ascentis (registered trademark) RP-Amide (particle size 5 μm, inner diameter×length=4.6 mm ×25 cm) manufactured by Merck corporation can be used as the analytical column.
In the measurement of the sample prepared by the above method, the absorbance of the peak at 369 nm obtained by the ultraviolet spectrophotometer of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane was measured. The sum of the obtained absorbance is converted into the weight ratio of dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane in 1, 3-butanediol using the formula "peak sum weight ratio (ppm) =coefficient×sum of absorbance" derived from the calibration curve.
By setting the peak and the weight ratio to 90 ppm or less, the generation of odor and the coloration under alkaline conditions of the 1, 3-butanediol product can be reduced.
From the viewpoint that the effect of the present invention is more remarkable, the peak and weight ratio is preferably 75 ppm or less, more preferably 60 ppm or less, further preferably 44 ppm or less, particularly preferably 30 ppm or less. The lower limit of the weight ratio is not particularly limited, and may be, for example, 1 ppm or more from the viewpoint of manufacturing cost.
In the HPLC analysis under the above conditions, the relative residence time of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxan can be confirmed, for example, by the following means: to 0.05/g of a solution obtained by diluting 1, 3-butanediol manufactured by KH Neochem Co., ltd. In such a manner that the weight concentration of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane to be synthesized separately reaches 300 ppm, 100. Mu.L of hydrochloric acid and 1000. Mu.L of a solution obtained by extracting with acetonitrile 5 mL in a DNPH column (INERTSEP MINI AERO DNPH, GL Sciences Co.) were added, the reaction was carried out at 45℃for 2 hours, the obtained reaction solution was diluted to 2 mL as a mobile phase used in HPLC analysis, and the peak of a dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane was measured by HPLC analysis under the above conditions.
The area ratio of the peak of 1, 3-butanediol in the gas chromatographic analysis under the following conditions is not particularly limited, but is preferably 99.5% or more, more preferably 99.7% or more, still more preferably 99.8% or more, and particularly preferably 99.9% or more, depending on the quality of the product required.
The measurement conditions for the gas chromatography in the present embodiment are preferably as follows.
[ Conditions for gas chromatography ]
Analytical column: column with stationary phase of dimethylpolysiloxane (length 30 m X inner diameter 0.25 mm X film thickness 0.25 μm)
Heating conditions: after heating from 80℃to 230℃at 5℃per minute, the mixture was kept at 230℃for 10 minutes
Sample introduction temperature: 250 DEG C
Carrier gas: nitrogen gas
Gas flow rate of column: 0.5 mL/min
Detector and detection temperature: hydrogen Flame Ionization Detector (FID), 250℃
[ Coloration under alkaline conditions ]
The 1, 3-butanediol product according to this embodiment has an advantage that coloration is not easily generated under alkaline conditions. The degree of coloration (b) of the b-color system (JISZ 8729) after heating the 1, 3-butanediol product of the present embodiment at 90 ℃ for 6 hours under alkaline conditions is not particularly limited, and for example, the average value of 3 measurements is preferably 4.4 or less, more preferably 4.1 or less, and particularly preferably 3.8 or less.
[ Method for producing 1, 3-butanediol product ]
(Raw materials)
The crude 1, 3-butanediol to be used as a raw material in the production of the 1, 3-butanediol product of the present embodiment is not particularly limited, and examples thereof include 1, 3-butanediol having a perceived odor, 1, 3-butanediol having an increased odor with time, and the like. Or 1, 3-butanediol colored in the preparation under alkaline conditions.
The area ratio of the peak of 1, 3-butanediol in the gas chromatography under the above specific conditions is preferably 99.5% or more, more preferably 99.6% or more, and even more preferably 99.7% or more, from the viewpoint of reducing the amount of impurities contained in the 1, 3-butanediol product as a raw material.
The method for producing crude 1, 3-butanediol as a raw material is not particularly limited, and for example, crude 1, 3-butanediol can be produced by a known method (see Japanese patent publication No. 3-80139, japanese patent application laid-open No. 7-258129, etc.). In addition, any of the following may be used: materials produced by a liquid-phase hydrogen reduction method of butyl aldol, materials produced by a hydrolysis method of 1, 3-butylene oxide, materials produced by a fermentation method using microorganisms or fungi, mixtures thereof, and the like. Among them, since the effect of the present invention tends to be more remarkable, it is preferable to use a reaction product obtained by a liquid-phase hydrogen reduction method of the aldol. In the liquid-phase hydrogen reduction method of butyl alcohol aldehyde, low boiling point compounds such as acetaldehyde, butyraldehyde, crotonaldehyde, methyl vinyl ketone, 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane, or their condensates, or acetals with 1, 3-butanediol, acetals with ethanol, or the like, which are considered as odor causative substances, are produced in the sub-zone, and it is difficult to completely remove them even by distillation. The odor causing substance includes a substance which itself is an odor source, a substance which becomes an odor substance by time-varying, heat-treating, chemical-treating, or the like, and the like.
In addition, a material from which alcohols such as ethanol, salts, and moisture, etc., as by-products, have been removed from a reaction product obtained by a hydrogen reduction method of a aldol, may also be used. The method for removing these components is not limited, and methods such as distillation and adsorption may be used.
In addition, the following may be used as crude 1, 3-butanediol: a material obtained by removing ethanol or the like as a by-product from a reaction product obtained by a hydrogen reduction method of a aldol by distillation; the fraction from which ethanol has been removed is subjected to further 1 or more known purification steps, for example, a step of adding an alkali metal compound (for example, sodium hydroxide, potassium hydroxide, or the like) and performing a heat treatment (see japanese patent No. 4559625, or the like). Crude 1, 3-butanediol is also commercially available.
The method for producing the 1, 3-butanediol product according to the present embodiment is not particularly limited, and for example, a method including the following steps may be used: a step (extraction step) of mixing crude 1, 3-butanediol with water and an organic solvent to separate the phases into an aqueous layer and an organic layer and then obtaining an aqueous layer containing 1, 3-butanediol; a step (hydrolysis step) of heat-treating the aqueous layer containing 1, 3-butanediol; a step of distilling off water from the heat-treated aqueous layer containing 1, 3-butanediol (dehydration distillation step); and a step of distilling off the low boiling point component from the 1, 3-butanediol after the water has been distilled off (low boiling point removal distillation step). The following describes each step.
[ Extraction procedure ]
The extraction step in the method for producing a 1, 3-butanediol product according to this embodiment is a step of mixing crude 1, 3-butanediol with water and an organic solvent, separating the phases into an aqueous layer and an organic layer, and obtaining an aqueous layer containing 1, 3-butanediol. Examples of the organic solvent include: aliphatic hydrocarbons such as hexane and heptane, cyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether and dibutyl ether, organic chlorides such as methylene chloride and chloroform, esters such as ethyl acetate and butyl acetate, ketones such as methyl isobutyl ketone, and the like, and among these, from the viewpoint of impurity removal, the cyclic aliphatic hydrocarbons are preferable, and methylcyclohexane is more preferable. These organic solvents may be used alone, or may be used by mixing at least 2 kinds of them at an arbitrary ratio. The amount of the organic solvent to be used is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the crude 1, 3-butanediol, from the viewpoint of extraction efficiency.
The amount of water to be used is preferably 20 to 400 parts by mass, more preferably 40 to 200 parts by mass, based on 100 parts by mass of the crude 1, 3-butanediol, from the viewpoint of extraction efficiency. The order of adding water and the organic solvent to the crude 1, 3-butanediol is not particularly limited. The temperature at which the water and the organic solvent are mixed with the crude 1, 3-butanediol is not particularly limited, but is preferably a temperature of 5 to 80℃and more preferably a temperature of 10 to 50℃from the viewpoint of extraction efficiency.
The mixing of the crude 1, 3-butanediol with water and the organic solvent can be carried out, for example, in a batch type or a continuous type.
In the case of batch-wise operation, for example, a method in which crude 1, 3-butanediol, water and an organic solvent are added to a mixing tank, stirred for preferably 10 seconds to 2 hours, and then allowed to stand for preferably 1 minute to 2 hours to separate the phases, thereby obtaining an aqueous layer containing 1, 3-butanediol, and the like are exemplified. The obtained aqueous layer containing 1, 3-butanediol may be repeatedly subjected to a further addition of an organic solvent to separate the phases, and then the aqueous layer containing 1, 3-butanediol is obtained, and the number of repetitions is preferably 1 to 3. In this case, the amount of the organic solvent to be added is preferably 10 to 300 parts by mass per 1 part by mass per 100 parts by mass of the crude 1, 3-butanediol.
As the apparatus for continuous extraction, a device commonly used for continuous extraction or the like, for example, a combination of a mixer and a settler, a spray tower, a packed tower, a tray tower or the like can be used, and a packed tower or a tray tower having 3 or more theoretical stages is particularly preferably used.
[ Hydrolysis Process ]
The hydrolysis step in the method for producing a1, 3-butanediol product according to this embodiment is a step of heat-treating the aqueous layer containing 1, 3-butanediol obtained in the extraction step. It is presumed that, by subjecting an aqueous layer containing 1, 3-butanediol to a heat treatment, an acetal compound or the like contained therein is hydrolyzed to become a low boiling point substance, and therefore, the low boiling point substance which is a cause of odor and a cause of coloration under alkaline conditions can be effectively removed in a subsequent distillation step. The mechanism of the present invention is not limited to the above.
The heating time in the hydrolysis step is not particularly limited, but is preferably 20 minutes to 9 hours, more preferably 1 to 6 hours, and still more preferably 1 to 3 hours. When the heating time is 20 minutes or longer, hydrolysis of the acetal compound or the like tends to proceed sufficiently, and when it is 9 hours or shorter, the cost for the heating treatment tends to be suppressed.
The heating temperature in the hydrolysis step is not particularly limited, but is preferably 60 to 130 ℃, more preferably 75 to 115 ℃, and still more preferably 90 to 100 ℃. When the heating temperature is 60 ℃ or higher, hydrolysis of an acetal compound or the like tends to proceed sufficiently, and when the heating temperature is 130 ℃ or lower, vaporization of water from an aqueous layer containing 1, 3-butanediol is suppressed, and the hydrolysis rate of an acetal compound or the like tends to be maintained.
The heat treatment apparatus in the hydrolysis step is not particularly limited, and examples thereof include continuous pipe type, batch type tank type, continuous tank type, and the like, and in the case of using a batch type, a batch type tank type is particularly preferable from the viewpoint of stirring efficiency.
[ Dehydration distillation Process ]
The dehydration distillation step in the method for producing a 1, 3-butanediol product according to the present embodiment is a step of distilling off water from the aqueous layer containing 1, 3-butanediol obtained in the hydrolysis step. Examples of distillation apparatuses used in the dehydration distillation step include perforated plate columns, bubble cap columns, and packed columns, and among these, packed columns having 7 to 40 theoretical stages are preferable. The distillation column may be 1 column or more than 2 columns. As conditions for distillation, the pressure at the top of the distillation column is preferably 5 to 20kPa, and the temperature at the bottom of the distillation column is preferably 120 to 160℃and more preferably 135 to 155 ℃. Specific examples of the dehydration distillation step include a method in which a water layer containing 1, 3-butanediol is continuously supplied from the top of a distillation column, a fraction containing a large amount of water is continuously withdrawn from the top of the column, and 1, 3-butanediol is continuously withdrawn from the bottom of the column.
[ Low boiling distillation Process ]
The low boiling point distillation step in the method for producing 1, 3-butanediol according to the present embodiment is a step of distilling off low boiling point components from the 1, 3-butanediol obtained in the dehydration distillation step. Examples of distillation apparatuses used in the low boiling distillation step include perforated plate columns, bubble cap columns, and packed columns, and among these, packed columns having 7to 40 theoretical stages are preferable. The distillation column may be 1 column or more than 2 columns. As conditions for distillation, the pressure at the top of the distillation column is preferably 1 to 20 kPa, and the temperature at the bottom of the distillation column is preferably 100 to 160℃and more preferably 110 to 140 ℃. Specific examples of the low boiling distillation step include a method in which 1, 3-butanediol is continuously supplied from the top of a distillation column, a fraction containing a relatively large amount of low boiling components is continuously withdrawn from the top of the column, and 1, 3-butanediol is continuously withdrawn from the bottom of the column.
The method for producing 1, 3-butanediol in the present embodiment is preferably a method in which the preferable ranges of the above steps are combined.
Examples (example)
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. As the crude 1, 3-butanediol to be used as a raw material, 1, 3-butanediol (product name: 1, 3-butanediol) manufactured by KH Neochem Co., ltd. In addition, various analyses and evaluations were performed as follows.
[ HPLC analysis ]
HPLC analysis of 1, 3-butanediol preparations was performed under the following conditions.
(Conditions for HPLC analysis)
Sample preparation: 2, 4-dinitrophenylhydrazine was extracted by adding acetonitrile 5mL to a 2, 4-dinitrophenylhydrazine cartridge (INERTSEP MINI AERO DNPH, GL Sciences Co.), 1000. Mu.L of the resulting solution and 0.2 mol/L of hydrochloric acid 100. Mu.L were added to 1, 3-butanediol 0.05 g and the reaction was carried out at 45℃for 2 hours. The reaction solution was diluted to 2mL with a mobile phase used in HPLC, and the diluted solution was used as a measurement sample.
Analysis device: agilent 1200Series manufactured by Agilent technologies Inc
A detector: agilent 1200Series UV-visible light detector G1314B manufactured by Agilent technologies Inc
Detection wavelength: 369 nm (nm)
Analytical column: SUPELCO (registered trademark) Ascentis (registered trademark) RP-Amide (particle size 5 μm, inner diameter. Times. Length=4.6 mm. Times.25. Cm) manufactured by Merck company
Analysis conditions: column temperature 40 DEG C
Mobile phase: acetonitrile/distilled water=50/50 (volume ratio)
Mobile phase flow rate: 0.4 mL/min
Sample injection conditions: 20. mu L (mu L)
Calibration curve: is prepared by using dinitrophenylhydrazine derivatives of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane which are synthesized separately.
SUPELCO (registered trademark) Ascentis (registered trademark) RP-Amide manufactured by Merck corporation used as an analytical column was a column in which palmitoamidopropyl group-modified silica gel (particle diameter 5 μm, inner diameter×length=4.6 mm ×25 cm, pore diameter 100 a, surface coverage 2.7 micromole/m 2, surface area 450 m 2/g, metal impurity less than 5 ppm, and carbon content 19.5%) was used as a stationary phase.
In the measurement of the sample prepared by the above method, the absorbance of the peak at 369 nm obtained by the ultraviolet spectrophotometer of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane was measured. The sum of the obtained absorbance was converted into the weight ratio of dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane in 1, 3-butanediol using the formula "peak sum weight ratio (ppm) =0.206×sum of absorbance" derived from the calibration curve. When the relative retention time of the peak of DNPH is 1.0, the peak (peaks A and B in FIG. 1) appearing in the range of 1.1 to 1.6 is set as the peak of dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane.
[ Gas chromatography analysis ]
The 1, 3-butanediol product as a subject was subjected to gas chromatography under the following conditions.
(Conditions for gas chromatography)
Analysis device: 7890B gas chromatography system manufactured by Agilent technologies
Analytical column: DB-WAX manufactured by Agilent technologies Co., ltd. (length 30 m. Times. Inner diameter 0.25. Times. Mm. Film thickness 0.25 μm)
Heating conditions: after heating from 80℃to 230℃at 5℃per minute, the mixture was kept at 230℃for 10 minutes
Sample introduction temperature: 250 DEG C
Carrier gas: nitrogen gas
Gas flow rate of column: 0.5 mL/min
Detector and detection temperature: hydrogen Flame Ionization Detector (FID), 250℃
Control mode: constant current
Split ratio: 50:1
Sample injection conditions: 1. mu L (mu L)
[ Odor test ]
For 1, 3-butanediol obtained in examples and comparative examples, odor tests were conducted according to the following 2 evaluation methods.
(Evaluation method of odor)
10% By weight aqueous 1, 3-butanediol solution 10g was added to a wide mouth glass bottle of 20 mL and the lid was closed and stirred vigorously at room temperature for 1 minute. The cover was opened to smell the odor and compared with a standard odor sample to determine the odor level of the sample. The number of evaluation persons was 7, and the average score of the evaluation results of the respective persons was calculated and used as the odor score.
(Evaluation method for odor recovery)
10 Wt% aqueous 1, 3-butanediol solution 10 g was added to a wide mouth glass bottle of 20 mL and the lid was closed and heated at 50℃for 3 days. Thereafter, the mixture was cooled to room temperature and stirred vigorously for 1 minute. The cover was opened to smell the odor and compared with a standard odor sample to determine the odor level of the sample. The number of evaluation persons was 7, and the average score of the evaluation results of each person was calculated and used as the score for odor recovery. The above test is referred to as an odor recovery test.
Scoring of
A10 wt% aqueous solution of1, 3-butanediol manufactured by KH Neochem Co., ltd was used as a standard odor sample, and the score of the sample was set to 5. The case where no odor was perceived was set as a score of1, and the case therebetween was set as scores of 2 to 4 in accordance with the following.
1: No bad smell is felt
2: Faintly perceived odor
3: Perceived weaker malodor
4: Perceived odor
5: Obviously feel bad smell
[ Alkaline coloring test ]
The 1, 3-butanediol obtained in examples and comparative examples was evaluated for coloration under alkaline conditions according to the following method.
(Conditions of alkaline coloring test)
To a 100mL heat-resistant Medium Bottle (Medium Bottle) were added water 13 g and potassium hydroxide 2g, mixed, and further 1, 3-butanediol 6 g as a target was added. Next, the heat-resistant medium bottle was immersed in a water bath, and heat treatment was performed at 90℃for 6 hours. After cooling to room temperature, the color degree (b) of the alkali-treated solution was measured by a color difference meter SE2000 manufactured by japan electrochromic corporation. The same procedure was performed 3 times, and the average score of the 3 measurement results was calculated and used as a score of chroma (b).
Example 1
(Extraction step)
1, 3-Butanediol 100 g, water 100 g and methylcyclohexane 100 g manufactured by KH Neochem Co., ltd were added to a 500 mL separable flask, and the mixture was stirred at a temperature of 10℃for 10 minutes at a rotation speed of 500 rpm and then allowed to stand for 5 minutes, so that the phases were separated into an aqueous layer and an organic layer. To the separated aqueous layer, methylcyclohexane 100 g was further added, and the same procedure was repeated 2 times.
(Hydrolysis step)
Then, the aqueous layer obtained in the extraction step was added to a three-necked flask equipped with a cooler, and heat treatment was performed at an oil bath temperature of 100℃for 1 hour.
(Dehydration distillation Process)
Then, the water layer after the heat treatment was added to an eggplant-shaped flask, and dehydrated and concentrated at an oil bath temperature of 150℃and 8 kPa for 30 minutes to obtain 87. 87 g of 1, 3-butanediol.
(Step of distilling off Low boiling)
The dehydrated and concentrated 1, 3-butanediol was subjected to low boiling distillation at an oil bath temperature of 120℃and a temperature of 1.2. 1.2 kPa by a distillation apparatus equipped with a Webster fractionation apparatus of 20 cm, whereby a distillate fraction having a weight percentage of 3% relative to the amount of the liquid fed was distilled off from the top of the distillation apparatus. As a result, a1, 3-butanediol product of 77 g was obtained.
As a result of HPLC analysis performed on the 1, 3-butanediol product, which was measured after the preparation of the sample in advance, the peak and weight ratio of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane were 44 ppm. As a result of gas chromatography under the above conditions, the area ratio of the 1, 3-butanediol peak was 99.7%.
The 1, 3-butanediol product was subjected to an odor test, and as a result, the odor was scored as 1, and the odor recovery was scored as 1. Further, as a result of the alkaline coloring test, the degree of coloration (b) after heating at 90 ℃ for 6 hours under alkaline conditions was 4.1.
These results are shown in table 1 for the 1, 3-butanediol preparation. Further, a diagram of HPLC analysis of the 1, 3-butanediol product of example 1 is shown in FIG. 1.
Example 2
The extraction process was performed in the same manner as in example 1, except that the temperature in the extraction step was 50 ℃. As a result of HPLC analysis after preparing a sample in advance, the obtained 1, 3-butanediol product had a peak and weight ratio of dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxane of 35 ppm. As a result of gas chromatography under the above conditions, the area ratio of the 1, 3-butanediol peak was 99.7%.
The 1, 3-butanediol product was subjected to an odor test, and as a result, the odor was scored as 1, and the odor recovery was scored as 1. Further, as a result of the alkaline coloring test, the degree of coloration (b) after heating at 90 ℃ for 6 hours under alkaline conditions was 4.0.
These results are shown in table 1 for the 1, 3-butanediol preparation.
Example 3
The procedure of example 1 was repeated except that the heat treatment time in the hydrolysis step was 3 hours. As a result of HPLC analysis under the following conditions, the peak and weight ratio of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxan, which was measured after preparing a sample in advance, were 23 ppm. As a result of gas chromatography under the above conditions, the area ratio of the 1, 3-butanediol peak was 99.7%.
The 1, 3-butanediol product was subjected to an odor test, and as a result, the odor was scored as 1, and the odor recovery was scored as 1. Further, as a result of the alkaline coloring test, the degree of coloration (b) after heating at 90 ℃ for 6 hours under alkaline conditions was 3.9.
These results are shown in table 1 for the 1, 3-butanediol preparation.
Example 4
The procedure of example 1 was repeated except that the temperature of the oil bath in the low boiling distillation step was 140 ℃. As a result of HPLC analysis under the following conditions, the peak and weight ratio of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxan, which was measured after preparing a sample in advance, were 30 ppm. As a result of gas chromatography under the above conditions, the area ratio of the 1, 3-butanediol peak was 99.5%.
The 1, 3-butanediol product was subjected to an odor test, and as a result, the odor was scored as 1, and the odor recovery was scored as 1. Further, as a result of the alkaline coloring test, the degree of coloration (b) after heating at 90 ℃ for 6 hours under alkaline conditions was 3.4.
These results are shown in table 1 for the 1, 3-butanediol preparation.
Example 5
The procedure of example 1 was repeated except that the heating time in the hydrolysis step was set to 30 minutes, and that the distillate fraction having a weight percentage of 0.06% relative to the amount of the liquid additive was distilled off from the top of the distillation apparatus in the low boiling point removal distillation step. As a result of HPLC analysis under the following conditions, the peak and weight ratio of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxan, which was measured after preparing a sample in advance, were 75 ppm with respect to the obtained 1, 3-butanediol product. As a result of gas chromatography under the above conditions, the area ratio of the 1, 3-butanediol peak was 99.7%.
The 1, 3-butanediol product was subjected to an odor test, and as a result, the odor was scored as 1 and the odor recovery was scored as 2. Further, as a result of the alkaline coloring test, the degree of coloration (b) after heating at 90 ℃ for 6 hours under alkaline conditions was 4.3.
These results are shown in table 1 for the 1, 3-butanediol preparation.
Comparative example 1
The procedure of example 1 was repeated except that the hydrolysis step and the low boiling distillation step were not performed and that the extractant in the extraction step was methyl isobutyl ketone. Details are shown below.
(Extraction step)
1, 3-Butanediol 100 g, water 100 g and methyl isobutyl ketone 100 g manufactured by KH Neochem Co., ltd.) were added to a 500 mL separable flask, and the mixture was stirred at a temperature of 10℃for 10 minutes at a rotation speed of 500rpm and then left to stand for 5 minutes, so that the phases were separated into an aqueous layer and an organic layer. To the separated aqueous layer, methyl isobutyl ketone 100 g was further added, and the same procedure was repeated 2 times.
(Dehydration distillation Process)
Then, the aqueous layer obtained in the extraction step was added to an eggplant-shaped flask, and dehydrated and concentrated at an oil bath temperature of 150℃and 8 kPa for 30 minutes to obtain 79. 79 g of 1, 3-butanediol.
As a result of HPLC analysis performed on the 1, 3-butanediol obtained in the dehydration distillation step after the preliminary preparation of the sample, the peak and weight ratio of the dinitrophenylhydrazine derivative of 2- (hydroxyethyl) -2, 6-dimethyl-1, 3-dioxan were 98 ppm.
The obtained 1, 3-butanediol was subjected to an odor test, and as a result, the odor was scored as 3 and the odor recovery was scored as 4. Further, as a result of the alkaline coloring test, the degree of coloration (b) after heating at 90 ℃ for 6 hours under alkaline conditions was 4.6.
These results are shown in Table 1 for 1, 3-butanediol.
Further, FIG. 2 shows a diagram of HPLC analysis of 1, 3-butanediol obtained in comparative example 1.
The present application is based on japanese patent application (japanese patent application No. 2021-084070) filed 5/18/2021, and the content of which is incorporated herein by reference.
[ Industrial applicability ]
The 1, 3-butanediol of the present invention is industrially useful as a raw material for synthetic resins, a raw material for surfactants, a solvent, an antifreeze, a raw material for cosmetics, and the like.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-084070 | 2021-05-18 | ||
| JP2021084070A JP7079874B1 (en) | 2021-05-18 | 2021-05-18 | Product 1,3-butylene glycol |
| CN202280006633.6A CN116323533B (en) | 2021-05-18 | 2022-05-18 | 1, 3-Butanediol products |
| PCT/JP2022/020607 WO2022244791A1 (en) | 2021-05-18 | 2022-05-18 | Product 1,3-butylene glycol |
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| CN202280006633.6A Division CN116323533B (en) | 2021-05-18 | 2022-05-18 | 1, 3-Butanediol products |
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| EP (1) | EP4177240A4 (en) |
| JP (1) | JP7079874B1 (en) |
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| KR20240054284A (en) | 2021-09-02 | 2024-04-25 | 케이에이치 네오켐 가부시키가이샤 | Process for preparing product 1,3-butylene glycol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3816549A (en) * | 1971-01-28 | 1974-06-11 | Celanese Corp | Purification of alkylene glycols |
| JPS6165834A (en) | 1984-09-07 | 1986-04-04 | Daicel Chem Ind Ltd | Purification of 1,3-butylene glycol |
| JP3369707B2 (en) | 1994-03-17 | 2003-01-20 | ダイセル化学工業株式会社 | Purification method of 1,3-butylene glycol |
| KR100595399B1 (en) * | 1998-08-07 | 2006-07-03 | 다이셀 가가꾸 고교 가부시끼가이샤 | High Purity 1,3-Butylene Glycol and Manufacturing Method Thereof |
| JP2003096006A (en) * | 2001-09-26 | 2003-04-03 | Kyowa Yuka Co Ltd | 1,3-butylene glycol and method for producing the same |
| JP2003252811A (en) | 2002-02-27 | 2003-09-10 | Kyowa Yuka Co Ltd | Method for producing 1,3-butylene glycol |
| US8445733B1 (en) * | 2011-07-26 | 2013-05-21 | Oxea Bishop Llc | 1,3 butylene glycol with reduced odor |
| EP2857377B1 (en) * | 2012-06-05 | 2019-05-08 | Mitsubishi Chemical Corporation | Production method for 1, 4-butanediol |
| WO2018183628A1 (en) | 2017-03-31 | 2018-10-04 | Genomatica, Inc. | Process and systems for obtaining 1,3-butanediol from fermentation broths |
| KR20190023466A (en) * | 2017-08-29 | 2019-03-08 | 한국화학연구원 | High purity 1,3-butanediol and its preparation method |
| CN108383684B (en) | 2018-03-28 | 2021-07-30 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of synthetic method and system of 1,3-butanediol |
| KR102682257B1 (en) | 2019-09-05 | 2024-07-08 | 주식회사 다이셀 | 1,3-butylene glycol products |
| JP6804601B1 (en) | 2019-09-05 | 2020-12-23 | 株式会社ダイセル | 1,3-butylene glycol products |
| CN110790634B (en) * | 2019-10-14 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method of 1, 3-butanediol |
| JP7345984B2 (en) | 2019-11-27 | 2023-09-19 | 株式会社吉野工業所 | trigger type liquid squirt |
| EP4083002A4 (en) * | 2019-12-28 | 2024-07-24 | Daicel Corporation | PROCESS FOR PRODUCING 1,3-BUTYLENE GLYCOL AND 1,3-BUTYLENE GLYCOL PRODUCT |
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| KR102550111B1 (en) | 2023-06-29 |
| US12091379B2 (en) | 2024-09-17 |
| EP4177240A4 (en) | 2024-05-22 |
| US20230227389A1 (en) | 2023-07-20 |
| EP4177240A1 (en) | 2023-05-10 |
| JP2022177654A (en) | 2022-12-01 |
| CN116323533B (en) | 2024-07-30 |
| TW202313538A (en) | 2023-04-01 |
| WO2022244791A1 (en) | 2022-11-24 |
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